WO2014092873A1 - Procédés et appareil de séparation de lignine dans les bioraffineries - Google Patents
Procédés et appareil de séparation de lignine dans les bioraffineries Download PDFInfo
- Publication number
- WO2014092873A1 WO2014092873A1 PCT/US2013/067434 US2013067434W WO2014092873A1 WO 2014092873 A1 WO2014092873 A1 WO 2014092873A1 US 2013067434 W US2013067434 W US 2013067434W WO 2014092873 A1 WO2014092873 A1 WO 2014092873A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lignin
- solid additive
- acid
- gypsum
- liquor
- Prior art date
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 284
- 238000000034 method Methods 0.000 title claims abstract description 144
- 238000000926 separation method Methods 0.000 title claims abstract description 54
- 230000008569 process Effects 0.000 title claims description 109
- 239000007787 solid Substances 0.000 claims abstract description 161
- 239000000654 additive Substances 0.000 claims abstract description 136
- 230000000996 additive effect Effects 0.000 claims abstract description 120
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229920002678 cellulose Polymers 0.000 claims abstract description 92
- 239000001913 cellulose Substances 0.000 claims abstract description 91
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 81
- 235000000346 sugar Nutrition 0.000 claims abstract description 67
- 239000010440 gypsum Substances 0.000 claims abstract description 62
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 62
- 150000008163 sugars Chemical class 0.000 claims abstract description 59
- 239000002028 Biomass Substances 0.000 claims abstract description 54
- 239000002904 solvent Substances 0.000 claims abstract description 54
- 239000002253 acid Substances 0.000 claims abstract description 49
- 230000007062 hydrolysis Effects 0.000 claims abstract description 49
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 49
- 238000005194 fractionation Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000002029 lignocellulosic biomass Substances 0.000 claims description 28
- 229920001732 Lignosulfonate Polymers 0.000 claims description 26
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 18
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 18
- 239000008103 glucose Substances 0.000 claims description 18
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 15
- 238000004064 recycling Methods 0.000 claims description 14
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- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
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- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 claims description 6
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 claims description 6
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- 239000005909 Kieselgur Substances 0.000 claims description 5
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- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 235000019312 arabinogalactan Nutrition 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 229940057324 biore Drugs 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229940095672 calcium sulfate Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000019621 digestibility Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
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- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 238000013341 scale-up Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- 235000011127 sodium aluminium sulphate Nutrition 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- XDRLEQYUIGRZLG-UHFFFAOYSA-M sodium;ethanol;hydroxide;hydrate Chemical compound O.[OH-].[Na+].CCO XDRLEQYUIGRZLG-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
- C13K1/04—Purifying
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Definitions
- the present invention generally relates to fractionation processes for converting biomass into fermentable sugars, cellulose, and lignin.
- Biomass refining (or biorefining) is becoming more prevalent in industry.
- Cellulose fibers and sugars, hemicellulose sugars, lignin, syngas, and derivatives of these intermediates are being used by many companies for chemical and fuel production.
- Underutilized lignocellulosic biomass feedstocks have the potential to be much cheaper than petroleum, on a carbon basis, as well as much better from an environmental life-cycle standpoint.
- Lignocellulosic biomass is the most abundant renewable material on the planet and has long been recognized as a potential feedstock for producing chemicals, fuels, and materials.
- Lignocellulosic biomass normally comprises primarily cellulose, hemicellulose, and lignin.
- Cellulose and hemicellulose are natural polymers of sugars, and lignin is an aromatic/aliphatic hydrocarbon polymer reinforcing the entire biomass network.
- Some forms of biomass e.g., recycled materials do not contain hemicellulose.
- Cellulose from biomass can be used in industrial cellulose applications directly, such as to make paper or other pulp-derived products.
- the cellulose can also be subjected to further processing to either modify the cellulose in some way or convert it into glucose.
- Hemicellulose sugars can be fermented to a variety of products, such as ethanol, or converted to other chemicals.
- Lignin from biomass has value as a solid fuel and also as an energy feedstock to produce liquid fuels, synthesis gas, or hydrogen; and as an intermediate to make a variety of polymeric compounds. Additionally, minor components such as proteins or rare sugars can be extracted and purified for specialty applications.
- fractionation is accomplished.
- An important example is traditional biomass pulping (to produce paper and related goods).
- Cellulose is recovered in high yields, but lignin is primarily consumed by oxidation and hemicellulose sugars are mostly degraded.
- Approximately half of the starting biomass is essentially wasted in this manufacturing process.
- State-of-the-art biomass-pretreatment approaches typically can produce high yields of hemicellulose sugars but suffer from moderate cellulose and lignin yields.
- thermochemical pathway converts the feedstock into syngas (CO and 3 ⁇ 4) through gasification or partial oxidation.
- Another thermochemical pathway converts biomass into liquid bio-oils through pyrolysis and separation. These are both high-temperature processes that intentionally destroy sugars in biomass.
- Sugars e.g., glucose and xylose
- sugars are desirable platform molecules because they can be fermented to a wide variety of fuels and chemicals, used to grow organisms or produce enzymes, converted catalytically to chemicals, or recovered and sold to the market.
- the cellulose and/or the hemicellulose in the biomass must be hydro lyzed into sugars. This is a difficult task because lignin and hemicelluloses are bound to each other by covalent bonds, and the three components are arranged inside the fiber wall in a complex manner. This recalcitrance explains the natural resistance of woody biomass to decomposition, and explains the difficulty to convert biomass to sugars at high yields.
- Fractionation of biomass into its principle components has several advantages. Fractionation of lignocellulosics leads to release of cellulosic fibers and opens the cell wall structure by dissolution of lignin and hemicellulose between the cellulose microfibrils. The fibers become more accessible for hydrolysis by enzymes. When the sugars in lignocellulosics are used as feedstock for fermentation, the process to open up the cell wall structure is often called “pretreatment.” Pretreatment can significantly impact the production cost of lignocellulosic ethanol.
- a common chemical pretreatment process employs a dilute acid, usually sulfuric acid, to hydrolyze and extract hemicellulose sugars and some lignin.
- a common physical pretreatment process employs steam explosion to mechanically disrupt the cellulose fibers and promote some separation of hemicellulose and lignin. Combinations of chemical and physical pretreatments are possible, such as acid pretreatment coupled with mechanical refining. It is difficult to avoid degradation of sugars. In some cases, severe pretreatments (i.e., high temperature and/or low pH) intentionally dehydrate sugars to furfural, levulinic acid, and related chemicals. Also, in common acidic pretreatment approaches, lignin handling is very problematic because acid-condensed lignin precipitates and forms deposits on surfaces throughout the process. [0012] One type of pretreatment that can overcome many of these
- Organosolv refers to the presence of an organic solvent for lignin, which allows the lignin to remain soluble for better lignin handling.
- organosolv pretreatment or pulping has employed ethanol-water solutions to extract most of the lignin but leave much of the
- An acid catalyst can be introduced into organosolv pretreatment to attempt to hydrolyze hemicellulose into monomers while still obtaining the solvent benefit.
- organosolv wisdom dictates that high delignification can be achieved, but that a substantial fraction of hemicellulose must be left in the solids because any catalyst added to hydrolyze the hemicellulose will necessarily degrade the sugars (e.g., to furfural) during extraction of residual lignin.
- fractionation with a solution of ethanol (or another solvent for lignin), water, and sulfur dioxide (S0 2 ) can simultaneously achieve several important objectives.
- the fractionation can be achieved at modest temperatures (e.g., 120-160°C).
- the S0 2 can be easily recovered and reused. This process is able to effectively fractionation many biomass species, including softwoods, hardwoods, agricultural residues, and waste biomass.
- the S0 2 hydro lyzes the hemicelluloses and reduces or eliminates troublesome lignin-based precipitates.
- ethanol leads to rapid impregnation of the biomass, so that neither a separate impregnation stage nor size reduction smaller than wood chips are needed, thereby avoiding electricity-consuming sizing operations.
- the dissolved hemicelluloses are neither dehydrated nor oxidized (Iakovlev, "S0 2 -ethanol-water fractionation of lignocellulosics," Ph.D. Thesis, Aalto Univ., Espoo, Finland, 2011). Cellulose is fully retained in the solid phase and can subsequently be hydrolyzed to glucose.
- the mixture of hemicellulose monomer sugars and cellulose-derived glucose may be used for production of bio fuels and chemicals.
- the dominant pulping process today is the Kraft process. Kraft pulping does not fractionate lignocellulosic material into its primary components. Instead, hemicellulose is degraded in a strong solution of sodium hydroxide with or without sodium sulfide. The cellulose pulp produced by the Kraft process is high quality, essentially at the expense of both hemicellulose and lignin.
- hemicelluloses to fermentable sugars and further compounded by sulfite pulping side products, such as furfural, methanol, acetic acid, and others fermentation inhibitors.
- Lignin is a major component of biomass. It is typically between 15-35 wt% (dry basis) of the biomass material. Lignin has good fuel value, similar to some types of coal.
- Lignin is a natural polymer and is an essential part of wood and other forms of cellulosic biomass, including agricultural crop residues such as sugarcane bagasse. Lignin performs multiple functions that are essential to the life of the plant, including transport of nutrition and durability of the biomass. Lignin imparts rigidity to the cell walls and acts as a binder, creating a flexible composite cellulose- hemicellulose-lignin material that is outstandingly resistant to impact, compression, and bending.
- lignin is the most abundant organic polymer in the plant world. Lignin is a very complex natural polymer with many random couplings, and therefore lignin has no exact chemical structure.
- the molecular structure of lignin consists primarily of carbon ring structures (benzene rings with methoxyl, hydroxyl, and propyl groups.
- lignin formulations include molecular weight, chemical composition, and the type and distribution of chemical functional groups.
- Lignin can be difficult to process in biorefmeries because it has a tendency to deposit on solid surfaces and cause plugging.
- lignin handling has always been known to be a challenge, there remains a need in the art for ways to either avoid lignin precipitation or to deal with it after it occurs.
- Other difficulties are caused by downstream fermentation inhibition caused by lignin, as well as lignin fragments and derivatives (e.g., phenolics, acids, and other compounds).
- the present invention addresses the aforementioned needs in the art.
- the invention provides a process for fractionating lignocellulosic biomass, the process comprising:
- the solid additive has a density of at least 1.5 g/cm 3 , such as at least 2.0 g/cm 3 .
- the solid additive may be introduced to the digestor as a slurry or dissolved in a solution.
- the solid additive is present in the digestor at a concentration of at least 0.1 g/L, at least 1 g/L, or at least 10 g/L.
- the solid additive is selected from the group consisting of metal sulfates, metal sulfate hydrates, metal sulfate derivatives, ammonium sulfate, ammonium sulfate derivatives, native lignin, acid-condensed lignin, sulfonated lignin, lignin derivatives, and combinations thereof.
- the solid additive is selected from the group consisting of anhydrite, calcium sulfate hemihydrate, calcium sulfate dihydrate (gypsum), and combinations thereof.
- the solid additive may comprise or consist essentially of gypsum.
- the solid additive may comprise or consist essentially of gypsum and lignin.
- the gypsum may be recycled gypsum that is generated following step (f).
- the lignin may be recycled lignin that is removed following step (f).
- the solid additive is selected from the group consisting of minerals, diatomaceous earth, silica, alumina, ash, zeolites, metal alums, ammonium alum, dust, cellulose, nanocellulose, sawdust, agricultural residue pith, biomass fines, and combinations thereof.
- At least a portion of the solid additive may combine, chemically or physically, with the lignin to form a lignin-additive complex that has a higher density than the density of the lignin.
- At least a portion of the solid additive may combine, chemically or physically, with the lignin to form a lignin-additive complex that has one or more of the following properties: (i) a higher settling rate than that of the lignin; (ii) a higher viscosity than that of the lignin; (iii) a higher ratio of density to viscosity compared to the lignin; and (iv) reduced tackiness compared to the lignin.
- Step (d) may be carried out prior to, simultaneously with, or following removal of the solvent for lignin from the liquor. Also, step (d) may be carried out prior to, simultaneously with, or following removal of the sulfur dioxide from the liquor.
- the solid additive is optionally recovered and recycled.
- Some variations provide a process for fractionating lignocellulosic biomass, the process comprising:
- step (d) recovering the hemicellulose; and (h) recycling at least a portion of the produced gypsum to step (d).
- the additive precursor or precursors comprises lime and the additive comprises gypsum, in certain embodiments of the invention.
- a process for fractionating lignocellulosic biomass includes the steps of:
- Some variations provide a process for fractionating lignocellulosic biomass, the process comprising:
- step (d) is carried out prior to, simultaneously with, or following removal of the solvent for lignin from the liquor. Also, step (d) may be carried out prior to, simultaneously with, or following removal of the sulfur dioxide from the liquor.
- the process may further include introducing a solid additive to the digestor.
- the solid additive introduced to the digestor may be the same as, or different than, the solid additive introduced to the hydrolysis reactor. Any of these solids additives may be recovered and recycled.
- the above-described or other variations provide methods of improving lignin separation during lignocellulosic biorefining, the method comprising the steps of (i) catalyzing fractionation or hydrolysis with an acid to release sugars into an acidified solution containing lignin, wherein the solution also contains a solvent for lignin; (ii) neutralizing the acidified solution with a base to form a salt in a neutralized solution; (iii) in a separation unit, separating the salt and the lignin, each in free or combined form, from the neutralized solution; and then (iv) recycling a portion of the salt and optionally a portion of the lignin to step (i) to combine, physically or chemically, with the lignin, to improve lignin separation in the separation unit.
- the separation unit may be selected from the group consisting of a filter, a membrane, a decanter, a clarifier, a hydrocyclone, and a centrifuge.
- the salt may be selected from the group consisting of metal sulfates, metal sulfate hydrates, metal sulfate derivatives, ammonium sulfate, ammonium sulfate derivatives, and combinations thereof.
- the salt may be selected from the group consisting of anhydrite, calcium sulfate hemihydrate, calcium sulfate dihydrate (gypsum), and combinations thereof.
- Some embodiments provide a method of improving lignin separation during lignocellulosic biorefining, the method comprising the steps of (i) catalyzing fractionation or hydrolysis with a sulfur-containing acid and/or sulfur dioxide to release sugars and lignin into an acidified solution, wherein the solution also contains a solvent for lignin; (ii) neutralizing the acidified solution with lime to form gypsum in a neutralized solution; (iii) in a separation unit, separating the gypsum and the lignin, individually or in combination, from the neutralized solution; and then (iv) recycling a portion of the gypsum and optionally a portion of the lignin to step (i) to combine, physically or chemically, with the lignin released in step (i), to improve lignin separation in the separation unit in step (iii).
- FIG. 1 depicts an exemplary process embodiment of the invention to fractionate biomass into cellulose, hemicellulose, and lignin with introduction and/or recycle of one or more solid additives at one or more locations to improve lignin separation.
- phase consisting of excludes any element, step, or ingredient not specified in the claim.
- phrase consists of (or variations thereof) appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
- phase consisting essentially of limits the scope of a claim to the specified elements or method steps, plus those that do not materially affect the basis and novel characteristic(s) of the claimed subject matter.
- the present invention in some variations, is premised on the discovery that lignin separation may be improved, to a surprising extent, by introducing certain additives directly or indirectly into the digestor and/or hydrolysis reactor, as a precursor to later lignin separation by (for example) sedimentation, centrifugation, or filtration, or other separation operations to increase the lignin separation efficiency.
- the invention provides a process for fractionating lignocellulosic biomass, the process comprising:
- the invention provides a process for fractionating lignocellulosic biomass, the process comprising:
- the acid or acid precursor may be a sulfur-containing acid or compound, such as (but not limited to) sulfur dioxide, sulfurous acid, sulfur trioxide, sulfuric acid, lignosulfonic acid, or combinations thereof. Other acids or acid precursors may be employed. An acid precursor will generate some amount of acid in situ, under the liquor conditions of the digestor.
- the solid additive has a density of at least 1.5 g/cm 3 , such as at least 2.0 g/cm 3 .
- the solid additive may be introduced to the digestor as a slurry or dissolved in a solution.
- the solid additive is present in the digestor at a concentration of at least 0.1 g/L, at least 1 g/L, or at least 10 g/L.
- the solid additive is selected from the group consisting of metal sulfates, metal sulfate hydrates, metal sulfate derivatives, ammonium sulfate, ammonium sulfate derivatives, native lignin, acid-condensed lignin, sulfonated lignin, lignin derivatives, and combinations thereof.
- the solid additive is selected from the group consisting of anhydrite, calcium sulfate hemihydrate, calcium sulfate dihydrate (gypsum), and combinations thereof.
- the solid additive may comprise or consist essentially of gypsum.
- the solid additive may comprise or consist essentially of gypsum and lignin.
- the gypsum may be recycled gypsum that is generated following step (f).
- the lignin may be recycled lignin that is removed following step (f).
- the solid additive is selected from the group consisting of minerals, diatomaceous earth, silica, alumina, ash, zeolites, metal alums, ammonium alum, dust, cellulose, nanocellulose, sawdust, agricultural residue pith, biomass fines, and combinations thereof.
- At least a portion of the solid additive may combine, chemically or physically, with the lignin to form a lignin-additive complex that has a higher density than the density of the lignin.
- At least a portion of the solid additive may combine, chemically or physically, with the lignin to form a lignin-additive complex that has one or more of the following properties: (i) a higher settling rate than that of the lignin; (ii) a higher viscosity than that of the lignin; (iii) a higher ratio of density to viscosity compared to the lignin; and (iv) reduced tackiness compared to the lignin.
- Step (d) may be carried out prior to, simultaneously with, or following removal of the solvent for lignin from the liquor. Also, step (d) may be carried out prior to, simultaneously with, or following removal of the sulfur dioxide from the liquor.
- the solid additive is optionally recovered and recycled.
- Some variations provide a process for fractionating lignocellulosic biomass, the process comprising:
- step (h) recycling at least a portion of the produced gypsum to step (d).
- the additive precursor or precursors comprises lime and the additive comprises gypsum, in certain embodiments of the invention.
- a process for fractionating lignocellulosic biomass includes the steps of:
- Some variations provide a process for fractionating lignocellulosic biomass, the process comprising:
- the acid or acid precursor may be a sulfur-containing acid or compound, such as (but not limited to) sulfur dioxide, sulfurous acid, sulfur trioxide, sulfuric acid, lignosulfonic acid, or combinations thereof. Other acids or acid precursors may be employed. An acid precursor will generate some amount of acid in situ, under the conditions of the hydrolysis reactor.
- step (d) is carried out prior to, simultaneously with, or following removal of the solvent for lignin from the liquor. Also, step (d) may be carried out prior to, simultaneously with, or following removal of the sulfur dioxide from the liquor.
- the process may further include introducing a solid additive to the digestor.
- the solid additive introduced to the digestor may be the same as, or different than, the solid additive introduced to the hydrolysis reactor. Any of these solids additives may be recovered and recycled.
- the above-described or other variations provide methods of improving lignin separation during lignocellulosic biorefining, the method comprising the steps of (i) catalyzing fractionation or hydrolysis with an acid to release sugars into an acidified solution containing lignin, wherein the solution also contains a solvent for lignin; (ii) neutralizing the acidified solution with a base to form a salt in a neutralized solution; (iii) in a separation unit, separating the salt and the lignin, each in free or combined form, from the neutralized solution; and then (iv) recycling a portion of the salt and optionally a portion of the lignin to step (i) to combine, physically or chemically, with the lignin, to improve lignin separation in the separation unit.
- the separation unit may be selected from the group consisting of a filter, a membrane, a decanter, a clarifier, a hydrocyclone, and a centrifuge.
- the salt may be selected from the group consisting of metal sulfates, metal sulfate hydrates, metal sulfate derivatives, ammonium sulfate, ammonium sulfate derivatives, and combinations thereof.
- the salt may be selected from the group consisting of anhydrite, calcium sulfate hemihydrate, calcium sulfate dihydrate (gypsum), and combinations thereof.
- Some embodiments provide a method of improving lignin separation during lignocellulosic biorefining, the method comprising the steps of (i) catalyzing fractionation or hydrolysis with a sulfur-containing acid and/or sulfur dioxide to release sugars and lignin into an acidified solution, wherein the solution also contains a solvent for lignin; (ii) neutralizing the acidified solution with lime to form gypsum in a neutralized solution; (iii) in a separation unit, separating the gypsum and the lignin, individually or in combination, from the neutralized solution; and then (iv) recycling a portion of the gypsum and optionally a portion of the lignin to step (i) to combine, physically or chemically, with the lignin released in step (i), to improve lignin separation in the separation unit in step (iii).
- the solid additive has a density that is higher than the density of lignin, that is, higher than about 1-1.5 g/cm 3 .
- the solid additive may have a density of about 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5 g/cm 3 or higher.
- the solid additive may be introduced to the hydrolysis reactor as a dry powder, a wet powder, a slurry, partially or completely dissolved in a solution, as an aqueous liquid, in ionic form (i.e. a salt that is dissociated as anions and cations), etc.
- ionic form i.e. a salt that is dissociated as anions and cations
- solid additive is meant to refer to the phase of the additive in isolation from the hydrolysis reactor or solution. Within the hydrolysis reactor itself, the additive is by no means limited to being a distinct solid phase.
- the solid additive contains sulfur, such as in the form of a sulfate salt.
- sulfur such as in the form of a sulfate salt.
- sulfur it is possible for that sulfur to be reactive with the lignin so that at least a portion of the sulfur reacts with lignin to generate sulfonated lignin.
- Sulfonated lignin may be advantageous for downstream separation efficiency, in some embodiments.
- the solid additive may be selected from the group consisting of metal sulfates, metal sulfate hydrates, metal sulfate derivatives, ammonium sulfate, ammonium sulfate derivatives, native lignin, acid-condensed lignin, sulfonated lignin, lignin derivatives, and combinations thereof.
- the solid additive is selected from the group consisting of anhydrite (anhydrous calcium sulfate), calcium sulfate
- hemihydrate calcium sulfate dihydrate (gypsum), and combinations thereof.
- the solid additive comprises gypsum.
- the solid additive may consist essentially of gypsum.
- the solid additive comprises gypsum and lignin.
- the solid additive may consist essentially of gypsum and lignin.
- gypsum may include, or consist entirely of, recycled gypsum that is generated following the step(s) of separating the gypsum and lignin and from the fermentable hemicellulosic sugars.
- lignin may include, or consist entirely of, recycled lignin that is generated following the step(s) of separating the gypsum and lignin from the fermentable hemicellulosic sugars.
- the solid additive may preferably be something other than gypsum.
- ammonia or an ammonium alkali is used as the neutralizing base, and ammonium sulfate is produced, when a preferred solid additive is ammonium sulfate.
- the solid additive is not introduced directly but rather generated in situ, such as by introducing a base to react a portion of the catalyst with the base to form the additive.
- a base for example lime could be introduced, wherein the lime reacts with some acid to form gypsum as the solid additive. It would also be possible to add two or components that react with each other (not with the catalyst) in situ to make the solid additive.
- the solid additive is selected from the group consisting of minerals, diatomaceous earth, silica, alumina, ash, zeolites, metal alums, ammonium alum, dust, cellulose, nanocellulose, sawdust, agricultural residue pith, biomass fines, and combinations thereof.
- a mineral is a naturally occurring solid chemical substance formed through biogeochemical processes, having characteristic chemical composition and highly ordered atomic structure. Any of the more than 4,000 known minerals, according to the International Mineralogical Association, may be utilized as the solid additive in this invention.
- Zeolites include any known natural or synthetic zeolites, which are microporous, aluminosilicate minerals. Examples include, but are not limited to, talc, dolomite , olivine, and perlite.
- Alums include any alums of general formula AM(S0 4 ) 2 /?H 2 0, where
- A is an alkali metal or ammonium
- M is a trivalent metal
- n is greater than 1 , such as from 6 to 20, e.g. 12.
- Exemplary alums include aluminum potassium sulfate ("potash alum” or simply "alum"), KA1(S0 4 ) 2 - 12H 2 0; soda alum,
- Other solid additives include cellulose of various origins and particle size, including nanocellulose, or cellulosic materials such as sawdust, agricultural residue pith (such as corn stover pith), or other biomass particles or particles derived from biomass.
- another material is introduced, such as a buffer, an emulsifier, a mixing agent, or flocculating agent.
- a buffer such as a buffer, an emulsifier, a mixing agent, or flocculating agent.
- polymer flocculating agents may be introduced.
- Polymers can flocculate colloidal suspensions generally through the mechanisms of charge neutralization, formation of patches of opposite charge and subsequent attraction, and bridging. Flocculation depends on the size of the polymer molecule both in solution and after adsorption, charge density, polymer concentration, presence of other electrolytes, and the mode of addition.
- the selected solid additive performs one or more of these functions to some extent.
- alum may act as a buffering agent as well as a flocculating agent.
- the solid additive combines, chemically or physically, with the lignin to form a lignin-additive complex that has one or more of the following properties, compared to the lignin: a higher density; a higher viscosity; a higher density/viscosity ratio; a higher settling rate; and/or reduced tackiness.
- the solid additive may be classified as a lignin detackifier, in some embodiments. Other rheological modification may be accomplished, to alter the physical or mechanical properties of the complex, compared to lignin alone.
- the solid additive may be present in the hydrolysis reactor at a concentration of at least 0.1 g/L, at least 1 g/L, or at least 10 g/L, such as about 0.2, 0.5, 0.8, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10, 11, 12, 15, 20 g/L or higher.
- the hydrolysis catalyst may be added and then the solid additive added to the reactor. Or, the solid additive may be added and then the hydrolysis catalyst added to the reactor. Or, these components may be simultaneously introduced.
- the process may further comprise recovering and recycling at least a portion of the hydrolysis catalyst, at least a portion of the solid additive, or both.
- the lignin-additive complex may be separated from solution using a variety of separation devices.
- the separation unit may be selected from filters, membranes, decanters, clarifiers, centrifuges, decanting centrifuges, cyclones, hydrocyclones, precipitators, electrostatic precipitators, evaporators, flash vessels, distillation columns, and so on.
- the lignin-additive complex may be recovered in solid form, in slurry form, or as a dilute solution in liquid.
- the lignin and additive may be recovered in combination, or they may be recovered separately, in one or multiple stages or units. When the lignin and additive are recovered together, a portion may be recycled back to the hydrolysis reactor (at least some should be purged at steady state to avoid lignin build-up).
- This disclosure describes processes and apparatus to efficiently fractionate any lignocellulosic-based biomass into its primary major components (cellulose, lignin, and if present, hemicellulose) so that each can be used in potentially distinct processes.
- An advantage of the process is that it produces cellulose-rich solids while concurrently producing a liquid phase containing a high yield of both hemicellulose sugars and lignin, and low quantities of lignin and hemicellulose degradation products.
- the flexible fractionation technique enables multiple uses for the products.
- the cellulose is highly reactive to cellulase enzymes for the
- the biomass feedstock may be selected from hardwoods, softwoods, forest residues, industrial wastes, pulp and paper wastes, consumer wastes, or combinations thereof.
- Some embodiments utilize agricultural residues, which include lignocellulosic biomass associated with food crops, annual grasses, energy crops, or other annually renewable feedstocks.
- Exemplary agricultural residues include, but are not limited to, corn stover, corn fiber, wheat straw, sugarcane bagasse, sugarcane straw, rice straw, oat straw, barley straw, miscanthus, energy cane straw/residue, or combinations thereof.
- lignocellulosic biomass means any material containing cellulose and lignin. Lignocellulosic biomass may also contain
- the biomass feedstock comprises both a lignocellulosic component (such as one described above) in addition to a sucrose-containing component (e.g., sugarcane or energy cane) and/or a starch component (e.g., corn, wheat, rice, etc.).
- a lignocellulosic component such as one described above
- sucrose-containing component e.g., sugarcane or energy cane
- a starch component e.g., corn, wheat, rice, etc.
- the biomass feedstock need not be, but may be, relatively dry.
- the biomass is in the form of a particulate or chip, but particle size is not critical in this invention.
- Reaction conditions and operation sequences may vary widely. Some embodiments employ conditions described in U.S. Patent No. 8,030,039, issued Oct. 4, 2011; U.S. Patent No. 8,038,842, issued Oct. 11, 2011; U.S. Patent No. 8,268,125, issued Sept. 18, 2012; and U.S. Patent App. Nos. 13/004,431; 12/234,286;
- a first process step is "cooking" (equivalently,
- hemicelluloses are dissolved and over 50% are completely hydrolyzed; cellulose is separated but remains resistant to hydrolysis; and part of the lignin is sulfonated into water-soluble lignosulfonates.
- the lignocellulosic material is processed in a solution (cooking liquor) of aliphatic alcohol, water, and sulfur dioxide.
- the cooking liquor preferably contains at least 10 wt%, such as at least 20 wt%, 30 wt%, 40 wt%, or 50 wt% of a solvent for lignin.
- the cooking liquor may contain about 30-70 wt% solvent, such as about 50 wt% solvent.
- the solvent for lignin may be an aliphatic alcohol, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1- pentanol, 1-hexanol, or cyclohexanol.
- the solvent for lignin may be an aromatic alcohol, such as phenol or cresol.
- Other lignin solvents are possible, such as (but not limited to) glycerol, methyl ethyl ketone, or diethyl ether. Combinations of more than one solvent may be employed.
- the solvent for lignin may be completely miscible, partially miscible, or immiscible with water, so that there may be more than one liquid phase.
- Potential process advantages arise when the solvent is miscible with water, and also when the solvent is immiscible with water.
- the solvent is water-miscible, a single liquid phase forms, so mass transfer of lignin and hemicellulose extraction is enhanced, and the downstream process must only deal with one liquid stream.
- the solvent is immiscible in water, the extractant mixture readily separates to form liquid phases, so a distinct separation step can be avoided or simplified. This can be advantageous if one liquid phase contains most of the lignin and the other contains most of the hemicellulose sugars, as this facilitates recovering the lignin from the hemicellulose sugars.
- the cooking liquor preferably contains sulfur dioxide and/or sulfurous acid (H 2 SO 3 ).
- the cooking liquor preferably contains S0 2 , in dissolved or reacted form, in a concentration of at least 3 wt%, preferably at least 6 wt%, more preferably at least 8 wt%, such as about 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt% or higher.
- the cooking liquor may also contain one or more species, separately from S0 2 , to adjust the pH.
- the pH of the cooking liquor is typically about 4 or less.
- Sulfur dioxide is a preferred acid catalyst, because it can be recovered easily from solution after hydrolysis. The majority of the S0 2 from the hydrolysate may be stripped and recycled back to the reactor. Recovery and recycling translates to less lime required compared to neutralization of comparable sulfuric acid, less solids to dispose of, and less separation equipment. The increased efficiency owing to the inherent properties of sulfur dioxide mean that less total acid or other catalysts may be required. This has cost advantages, since sulfuric acid can be expensive. Additionally, and quite significantly, less acid usage also will translate into lower costs for a base (e.g., lime) to increase the pH following hydrolysis, for downstream operations. Furthermore, less acid and less base will also mean substantially less generation of waste salts (e.g., gypsum) that may otherwise require disposal.
- a base e.g., lime
- an additive may be included in amounts of about 0.1 wt% to 10 wt% or more to increase cellulose viscosity.
- Exemplary additives include ammonia, ammonia hydroxide, urea, anthraquinone, magnesium oxide, magnesium hydroxide, sodium hydroxide, and their derivatives.
- the cooking is performed in one or more stages using batch or continuous digestors. Solid and liquid may flow cocurrently or countercurrently, or in any other flow pattern that achieves the desired fractionation.
- the cooking reactor may be internally agitated, if desired.
- the cooking conditions are varied, with temperatures from about 65°C to 175°C, for example 75°C, 85°C, 95°C, 105°C, 115°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 165°C or 170°C, and corresponding pressures from about 1 atmosphere to about 15 atmospheres in the liquid or vapor phase.
- the cooking time of one or more stages may be selected from about 15 minutes to about 720 minutes, such as about 30, 45, 60, 90, 120, 140, 160, 180, 250, 300, 360, 450, 550, 600, or 700 minutes.
- the cooking liquor to lignocellulosic material ratio may be selected from about 1 to about 10, such as about 2, 3, 4, 5, or 6.
- biomass is digested in a pressurized vessel with low liquor volume (low ratio of cooking liquor to lignocellulosic material), so that the cooking space is filled with ethanol and sulfur dioxide vapor in equilibrium with moisture.
- the cooked biomass is washed in alcohol-rich solution to recover lignin and dissolved hemicelluloses, while the remaining pulp is further processed.
- the process of fractionating lignocellulosic material comprises vapor-phase cooking of
- lignocellulosic material with aliphatic alcohol (or other solvent for lignin), water, and sulfur dioxide. See, for example, U.S. Patent Nos. 8,038,842 and 8,268,125 which are incorporated by reference herein.
- sulfur dioxide may be present as sulfurous acid in the extract liquor.
- sulfur dioxide is generated in situ by introducing sulfurous acid, sulfite ions, bisulfite ions, combinations thereof, or a salt of any of the foregoing. Excess sulfur dioxide, following hydrolysis, may be recovered and reused.
- sulfur dioxide is saturated in water (or aqueous solution, optionally with an alcohol) at a first temperature, and the hydrolysis is then carried out at a second, generally higher, temperature.
- sulfur dioxide is sub-saturated.
- sulfur dioxide is super-saturated.
- sulfur dioxide concentration is selected to achieve a certain degree of lignin sulfonation, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% sulfur content.
- S0 2 reacts chemically with lignin to form stable lignosulfonic acids which may be present both in the solid and liquid phases.
- the concentration of sulfur dioxide, additives, and aliphatic alcohol (or other solvent) in the solution and the time of cook may be varied to control the yield of cellulose and hemicellulose in the pulp.
- the concentration of sulfur dioxide and the time of cook may be varied to control the yield of lignin versus lignosulfonates in the hydrolysate.
- the concentration of sulfur dioxide, temperature, and the time of cook may be varied to control the yield of fermentable sugars.
- the liquid and solid phases are separated. Conditions for the separation may be selected to minimize the reprecipitation of the extracted lignin on the solid phase. This is favored by conducting separation or washing at a temperature of at least the glass-transition temperature of lignin (about 120°C).
- the physical separation can be accomplished either by transferring the entire mixture to a device that can carry out the separation and washing, or by removing only one of the phases from the reactor while keeping the other phase in place.
- the solid phase can be physically retained by appropriately sized screens through which liquid can pass. The solid is retained on the screens and can be kept there for successive so lid- wash cycles. Alternately, the liquid may be retained and solid phase forced out of the reaction zone, with centrifugal or other forces that can effectively transfer the solids out of the slurry. In a continuous system, countercurrent flow of solids and liquid can accomplish the physical separation.
- the recovered solids normally will contain a quantity of lignin and sugars, some of which can be removed easily by washing.
- the washing-liquid composition can be the same as or different than the liquor composition used during fractionation. Multiple washes may be performed to increase effectiveness.
- one or more washes are performed with a composition including a solvent for lignin, to remove additional lignin from the solids, followed by one or more washes with water to displace residual solvent and sugars from the solids.
- Recycle streams such as from solvent-recovery operations, may be used to wash the solids.
- a solid phase and at least one liquid phase are obtained.
- the solid phase contains substantially undigested cellulose.
- a single liquid phase is usually obtained when the solvent and the water are miscible in the relative proportions that are present.
- the liquid phase contains, in dissolved form, most of the lignin originally in the starting lignocellulosic material, as well as soluble monomeric and oligomeric sugars formed in the hydrolysis of any hemicellulose that may have been present.
- Multiple liquid phases tend to form when the solvent and water are wholly or partially immiscible.
- the lignin tends to be contained in the liquid phase that contains most of the solvent.
- Hemicellulose hydrolysis products tend to be present in the liquid phase that contains most of the water.
- hydrolysate from the cooking step is subjected to pressure reduction.
- Pressure reduction may be done at the end of a cook in a batch digestor, or in an external flash tank after extraction from a continuous digestor, for example.
- the flash vapor from the pressure reduction may be collected into a cooking liquor make-up vessel.
- the flash vapor contains substantially all the unreacted sulfur dioxide which may be directly dissolved into new cooking liquor.
- the cellulose is then removed to be washed and further treated as desired.
- a process washing step recovers the hydrolysate from the cellulose.
- the washed cellulose is pulp that may be used for various purposes (e.g., paper or nanocellulose production).
- the weak hydrolysate from the washer continues to the final reaction step; in a continuous digestor this weak hydrolysate may be combined with the extracted hydrolysate from the external flash tank.
- washing and/or separation of hydrolysate and cellulose-rich solids is conducted at a temperature of at least about 100°C, 110°C, or 120°C.
- the washed cellulose may also be used for glucose production via cellulose hydrolysis with enzymes or acids.
- the hydrolysate may be further treated in one or multiple steps to hydro lyze the oligomers into monomers. This step may be conducted before, during, or after the removal of solvent and sulfur dioxide.
- the solution may or may not contain residual solvent (e.g. alcohol).
- sulfur dioxide is added or allowed to pass through to this step, to assist hydrolysis.
- an acid such as sulfurous acid or sulfuric acid is introduced to assist with hydrolysis.
- the hydrolysate is autohydrolyzed by heating under pressure. In some embodiments, no additional acid is introduced, but lignosulfonic acids produced during the initial cooking are effective to catalyze hydrolysis of hemicellulose oligomers to monomers.
- this step utilizes sulfur dioxide, sulfurous acid, sulfuric acid at a concentration of about 0.01 wt% to 30 wt%, such as about 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, or 20 wt%.
- This step may be carried out at a temperature from about 100°C to 220°C, such as about 1 10°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, or 210°C. Heating may be direct or indirect to reach the selected temperature.
- the reaction step produces fermentable sugars which can then be concentrated by evaporation to a fermentation feedstock. Concentration by evaporation may be accomplished before, during, or after the treatment to hydrolyze oligomers.
- the final reaction step may optionally be followed by steam stripping of the resulting hydrolysate to remove and recover sulfur dioxide and alcohol, and for removal of potential fermentation-inhibiting side products.
- the evaporation process may be under vacuum or pressure, from about -0.1 atmospheres to about 10 atmospheres, such as about 0.1 atm, 0.3 atm, 0.5 atm, 1.0 atm, 1.5 atm, 2 atm, 4 atm, 6 atm, or 8 atm.
- Recovering and recycling the sulfur dioxide may utilize separations such as, but not limited to, vapor-liquid disengagement (e.g. flashing), steam stripping, extraction, or combinations or multiple stages thereof.
- Various recycle ratios may be practiced, such as about 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.95, or more.
- about 90-99% of initially charged S0 2 is readily recovered by distillation from the liquid phase, with the remaining 1-10% (e.g., about 3-5%) of the S0 2 primarily bound to dissolved lignin in the form of lignosulfonates.
- the evaporation step utilizes an integrated alcohol stripper and evaporator.
- Evaporated vapor streams may be segregated so as to have different concentrations of organic compounds in different streams.
- Evaporator condensate streams may be segregated so as to have different concentrations of organic compounds in different streams.
- Alcohol may be recovered from the evaporation process by condensing the exhaust vapor and returning to the cooking liquor make-up vessel in the cooking step. Clean condensate from the evaporation process may be used in the washing step.
- an integrated alcohol stripper and evaporator system wherein aliphatic alcohol is removed by vapor stripping, the resulting stripper product stream is concentrated by evaporating water from the stream, and evaporated vapor is compressed using vapor compression and is reused to provide thermal energy.
- the hydrolysate from the evaporation and final reaction step contains mainly fermentable sugars but may also contain lignin depending on the location of lignin separation in the overall process configuration.
- the hydrolysate may be concentrated to a concentration of about 5 wt% to about 60 wt% solids, such as about 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt% or 55 wt% solids.
- the hydrolysate contains fermentable sugars.
- Fermentable sugars are defined as hydrolysis products of cellulose, galactoglucomannan, glucomannan, arabinoglucuronoxylans, arabinogalactan, and glucuronoxylans into their respective short-chained oligomers and monomer products, i.e., glucose, mannose, galactose, xylose, and arabinose.
- the fermentable sugars may be recovered in purified form, as a sugar slurry or dry sugar solids, for example. Any known technique may be employed to recover a slurry of sugars or to dry the solution to produce dry sugar solids.
- the fermentable sugars are fermented to produce biochemicals or biofuels such as (but by no means limited to) ethanol, isopropanol, acetone, 1-butanol, isobutanol, lactic acid, succinic acid, or any other fermentation products.
- biochemicals or biofuels such as (but by no means limited to) ethanol, isopropanol, acetone, 1-butanol, isobutanol, lactic acid, succinic acid, or any other fermentation products.
- Some amount of the fermentation product may be a microorganism or enzymes, which may be recovered if desired.
- the fermentation will employ bacteria, such as Clostridia bacteria
- bacteria such as Clostridia bacteria
- the residual S0 2 i.e., following removal of most of it by stripping
- the oxidation may be accomplished by adding an oxidation catalyst, such as FeS04-7H 2 0, that oxidizes sulfite ions to sulfate ions, which is a well-known practice for fermentation to
- the process further comprises recovering the lignin as a co-product.
- the sulfonated lignin may also be recovered as a co-product.
- the process further comprises combusting or gasifying the sulfonated lignin, recovering sulfur contained in the sulfonated lignin in a gas stream comprising reclaimed sulfur dioxide, and then recycling the reclaimed sulfur dioxide for reuse.
- the process lignin separation step is for the separation of lignin from the hydrolysate and can be located before or after the final reaction step and evaporation. If located after, then lignin will precipitate from the hydrolysate since alcohol has been removed in the evaporation step.
- the remaining water-soluble lignosulfonates may be precipitated by converting the hydrolysate to an alkaline condition (pH higher than 7) using, for example, an alkaline earth oxide, preferably calcium oxide (lime).
- the combined lignin and lignosulfonate precipitate may be filtered.
- the lignin and lignosulfonate filter cake may be dried as a co-product or burned or gasified for energy production.
- the hydrolysate from filtering may be recovered and sold as a concentrated sugar solution product or further processed in a subsequent fermentation or other reaction step.
- Native (non-sulfonated) lignin is hydrophobic, while lignosulfonates are hydrophilic. Hydrophilic lignosulfonates may have less propensity to clump, agglomerate, and stick to surfaces. Even lignosulfonates that do undergo some condensation and increase of molecular weight, will still have an HSO 3 group that will contribute some solubility (hydrophilic).
- the soluble lignin precipitates from the hydrolysate after solvent has been removed in the evaporation step.
- reactive lignosulfonates are selectively precipitated from hydrolysate using excess lime (or other base, such as ammonia) in the presence of aliphatic alcohol.
- hydrated lime is used to precipitate lignosulfonates.
- part of the lignin is precipitated in reactive form and the remaining lignin is sulfonated in water-soluble form.
- the process fermentation and distillation steps are intended for the production of fermentation products, such as alcohols or organic acids.
- the hydrolysate contains mainly fermentable sugars in water solution from which any fermentation inhibitors have been preferably removed or neutralized.
- the hydrolysate is fermented to produce dilute alcohol or organic acids, from 1 wt% to 20 wt% concentration.
- the dilute product is distilled or otherwise purified as is known in the art.
- alcohol such as ethanol
- some of it may be used for cooking liquor makeup in the process cooking step.
- a distillation column stream such as the bottoms, with or without evaporator condensate, may be reused to wash cellulose.
- lime may be used to dehydrate product alcohol.
- Side products may be removed and recovered from the hydrolysate. These side products may be isolated by processing the vent from the final reaction step and/or the condensate from the evaporation step. Side products include furfural, hydroxymethyl furfural (HMF), methanol, acetic acid, and lignin-derived compounds, for example.
- the cellulose-rich material is highly reactive in the presence of industrial cellulase enzymes that efficiently break the cellulose down to glucose monomers. It has been found experimentally that the cellulose-rich material, which generally speaking is highly delignified, rapidly hydrolyzes to glucose with relatively low quantities of enzymes.
- the cellulose-rich solids may be converted to glucose with at least 80% yield within 24 hours at 50°C and 2 wt% solids, in the presence of a cellulase enzyme mixture in an amount of no more than 15 filter paper units (FPU) per g of the solids. In some embodiments, this same conversion requires no more than 5 FPU per g of the solids.
- FPU filter paper units
- the glucose may be fermented to an alcohol, an organic acid, or another fermentation product.
- the glucose may be used as a sweetener or isomerized to enrich its fructose content.
- the glucose may be used to produce baker's yeast.
- the glucose may be catalytically or thermally converted to various organic acids and other materials.
- the cellulose-rich material is further processed into one more cellulose products.
- Cellulose products include market pulp, dissolving pulp (also known as a-cellulose), fluff pulp, purified cellulose, paper, paper products, and so on. Further processing may include bleaching, if desired. Further processing may include modification of fiber length or particle size, such as when producing nanocellulose or nanofibrillated or microfibrillated cellulose. It is believed that the cellulose produced by this process is highly amenable to derivatization chemistry for cellulose derivatives and cellulose-based materials such as polymers.
- hemicellulose When hemicellulose is present in the starting biomass, all or a portion of the liquid phase contains hemicellulose sugars and soluble oligomers. It is preferred to remove most of the lignin from the liquid, as described above, to produce a fermentation broth which will contain water, possibly some of the solvent for lignin, hemicellulose sugars, and various minor components from the digestion process. This fermentation broth can be used directly, combined with one or more other
- fermentation streams or further treated.
- Further treatment can include sugar concentration by evaporation; addition of glucose or other sugars (optionally as obtained from cellulose saccharification); addition of various nutrients such as salts, vitamins, or trace elements; pH adjustment; and removal of fermentation inhibitors such as acetic acid and phenolic compounds.
- the choice of conditioning steps should be specific to the target product(s) and microorganism(s) employed.
- hemicellulose sugars are not fermented but rather are recovered and purified, stored, sold, or converted to a specialty product.
- Xylose for example, can be converted into xylitol.
- a lignin product can be readily obtained from a liquid phase using one or more of several methods.
- One simple technique is to evaporate off all liquid, resulting in a solid lignin-rich residue. This technique would be especially
- Another method is to cause the lignin to precipitate out of solution.
- Some of the ways to precipitate the lignin include (1) removing the solvent for lignin from the liquid phase, but not the water, such as by selectively evaporating the solvent from the liquid phase until the lignin is no longer soluble; (2) diluting the liquid phase with water until the lignin is no longer soluble; and (3) adjusting the temperature and/or pH of the liquid phase. Methods such as centrifugation can then be utilized to capture the lignin.
- Lignin produced in accordance with the invention can be used as a fuel.
- lignin is similar in energy content to coal. Lignin can act as an oxygenated component in liquid fuels, to enhance octane while meeting standards as a renewable fuel.
- the lignin produced herein can also be used as polymeric material, and as a chemical precursor for producing lignin derivatives.
- the sulfonated lignin may be sold as a lignosulfonate product, or burned for fuel value.
- the present invention also provides systems configured for carrying out the disclosed processes, and compositions produced therefrom. Any stream generated by the disclosed processes may be partially or completed recovered, purified or further treated, and/or marketed or sold.
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Abstract
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BR112015013438A BR112015013438A2 (pt) | 2012-12-11 | 2013-10-30 | processo para fracionar biomassa lignocelulósica; e método para aprimorar a separação de lignina durante biorrefinamento lignocelulósico |
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US201261735738P | 2012-12-11 | 2012-12-11 | |
US61/735,738 | 2012-12-11 | ||
US14/066,534 | 2013-10-29 | ||
US14/066,534 US9322072B2 (en) | 2012-12-11 | 2013-10-29 | Processes and apparatus for lignin separation in biorefineries |
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WO2014092873A1 true WO2014092873A1 (fr) | 2014-06-19 |
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PCT/US2013/067434 WO2014092873A1 (fr) | 2012-12-11 | 2013-10-30 | Procédés et appareil de séparation de lignine dans les bioraffineries |
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US (2) | US9322072B2 (fr) |
BR (1) | BR112015013438A2 (fr) |
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DE102014221238A1 (de) * | 2014-10-20 | 2016-04-21 | Mpg Max-Planck-Gesellschaft Zur Förderung Der Wissenschaften E.V. | Verfahren zur Fällung von Lignin aus Organosolv-Kochlaugen |
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WO2019090414A1 (fr) | 2017-11-09 | 2019-05-16 | Iogen Corporation | Prétraitement à basse température à l'aide de dioxyde de soufre |
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US11118017B2 (en) | 2019-11-13 | 2021-09-14 | American Process International LLC | Process for the production of bioproducts from lignocellulosic material |
CN112058186A (zh) * | 2020-08-03 | 2020-12-11 | 中国林业科学研究院林产化学工业研究所 | 一种木质素纳米微球的制备方法 |
EP3960816B1 (fr) | 2020-08-25 | 2024-04-03 | Indian Oil Corporation Limited | Procédé de valorisation de flux de déchets de bioéthanol 2g |
IT202200003134A1 (it) * | 2022-02-21 | 2023-08-21 | Alter Eco Pulp S R L | Metodo di estrazione della cellulosa da biomasse di scarto |
CN115109271B (zh) * | 2022-08-10 | 2023-07-25 | 广州楹鼎生物科技有限公司 | 一种植物纤维原料生物炼制的方法及其所用装置 |
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- 2013-10-29 US US14/066,534 patent/US9322072B2/en active Active - Reinstated
- 2013-10-30 BR BR112015013438A patent/BR112015013438A2/pt not_active IP Right Cessation
- 2013-10-30 WO PCT/US2013/067434 patent/WO2014092873A1/fr active Application Filing
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US20160237102A1 (en) | 2016-08-18 |
BR112015013438A2 (pt) | 2017-07-11 |
US20140163210A1 (en) | 2014-06-12 |
US9322072B2 (en) | 2016-04-26 |
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